TW202200674A - Addition-reaction-curable organo-polysiloxane composition, release paper, and release film - Google Patents
Addition-reaction-curable organo-polysiloxane composition, release paper, and release film Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
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Abstract
Description
本發明是有關於一種能夠以少的鉑觸媒量進行硬化的加成反應硬化型有機聚矽氧烷組成物。更詳細而言，提供一種賦予剝離紙及剝離膜用的硬化皮膜的加成反應硬化型有機聚矽氧烷組成物。The present invention relates to an addition reaction hardening type organopolysiloxane composition which can be hardened with a small amount of platinum catalyst. In more detail, the addition reaction hardening type organopolysiloxane composition which provides the hardened film for release papers and release films is provided.
先前，為了防止紙或塑膠等片狀基材與黏著材料的接著、固著，而於基材表面形成有機聚矽氧烷組成物的硬化皮膜以賦予剝離特性。作為於基材面形成有機聚矽氧烷硬化皮膜的方法，已知下述專利文獻1～專利文獻3中記載的方法。 （1）將鉑系化合物作為觸媒並使含有烯基的有機聚矽氧烷與有機氫聚矽氧烷進行加成反應從而形成剝離性皮膜的方法（專利文獻1：日本專利特開昭47-32072號公報） （2）將有機金屬鹽作為觸媒並使具有羥基或烷氧基之類的官能基的有機聚矽氧烷進行縮合反應從而形成剝離性皮膜的方法（專利文獻2：日本專利特公昭35-13709號公報） （3）使用紫外線或電子束使含有丙烯酸基的有機聚矽氧烷與光反應起始劑進行自由基聚合從而形成剝離性皮膜的方法（專利文獻3：日本專利特開昭54-162787號公報） 所述內容中，（1）專利文獻1中記載的鉑系觸媒的硬化性優異，能夠應對自低速剝離到高速剝離的各種剝離特性的要求。因此，鉑觸媒廣泛用於藉由加成反應形成剝離性皮膜的方法。Previously, in order to prevent adhesion and fixation between sheet-like substrates such as paper or plastic and adhesive materials, a hardened film of an organopolysiloxane composition was formed on the surface of the substrate to impart peeling properties. As a method of forming a cured organopolysiloxane film on the base material surface, the methods described in the following Patent Documents 1 to 3 are known. (1) A method of forming a peelable film by addition-reacting an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane using a platinum-based compound as a catalyst (Patent Document 1: Japanese Patent Laid-Open No. 47 - Bulletin No. 32072) (2) A method of forming a peelable film by condensing an organopolysiloxane having a functional group such as a hydroxyl group or an alkoxy group using an organometallic salt as a catalyst (Patent Document 2: Japanese Patent Publication No. Sho 35- Bulletin No. 13709) (3) A method of forming a peelable film by radically polymerizing an acrylic group-containing organopolysiloxane and a photoreaction initiator using ultraviolet rays or electron beams (Patent Document 3: Japanese Patent Laid-Open No. 54-162787 ) ) Among the above, (1) the platinum-based catalyst described in Patent Document 1 is excellent in curability, and can meet the requirements of various peeling properties from low-speed peeling to high-speed peeling. Therefore, platinum catalysts are widely used in a method for forming a peelable film by an addition reaction.
先前，剝離紙或剝離膜用的有機聚矽氧烷組成物中所含的鉑族金屬系觸媒的量以鉑族金屬濃度計大多為60質量ppm～400質量ppm。鉑濃度低於所述下限值時，硬化反應無法充分進行，硬化皮膜變軟。另外，殘留的Si-H基量變多，剝離力變高。而且，未反應的原料有機聚矽氧烷存在並成為轉移成分，因此有機聚矽氧烷有可能轉移到貼合在剝離紙上的黏著劑面上，從而引起黏著力的降低。Conventionally, the amount of the platinum group metal-based catalyst contained in the organopolysiloxane composition for a release paper or a release film is often 60 to 400 mass ppm in terms of the platinum group metal concentration. When the platinum concentration is lower than the lower limit, the curing reaction does not proceed sufficiently, and the cured film becomes soft. In addition, the amount of remaining Si—H groups increases, and the peeling force increases. Furthermore, since the unreacted raw material organopolysiloxane exists and becomes a transfer component, there is a possibility that the organopolysiloxane is transferred to the surface of the adhesive attached to the release paper, thereby causing a decrease in the adhesive force.
而且，鉑族金屬是稀有的貴金屬，因此價格高，鉑觸媒在製造剝離紙或剝離膜的成本中所佔的比例大。因此，減少鉑族金屬系觸媒關係到低價格化。除此之外，基材中亦存在包含氮化合物、硫化合物、磷化合物等成為鉑族金屬系觸媒的觸媒毒的成分者，觸媒毒成分有時會與鉑族金屬鍵結，從而無法藉由加成反應進行硬化。Furthermore, since platinum group metals are rare and precious metals, they are expensive, and platinum catalysts account for a large proportion of the cost of manufacturing release paper or release film. Therefore, reduction of platinum group metal-based catalysts is related to cost reduction. In addition, the base material also contains nitrogen compounds, sulfur compounds, phosphorus compounds and other components that become catalyst poisons of platinum group metal catalysts. Hardening is not possible by addition reactions.
因此，要求以少的鉑量形成剝離性皮膜的方法。例如專利文獻4及專利文獻5中記載了以下組成物。 （4）矽酮組成物，包含每一分子具有至少兩個與矽原子鍵結的烯基的聚有機矽氧烷、在末端及側鏈具有SiH基的氫化有機矽氧烷、以及作為黏著性調節體系的MDVi Q樹脂及矽氫化抑制劑（所述中，M為R3 SiO1/2 ，DVi 為RPSiO2/2 ，,Q為SiO4/2 ，R分別獨立地為不具有脂肪族不飽和鍵的碳原子數1～12的未經取代或經取代的一價烴基，P為由-(CH2 )n -CH=CH2 （n為0～6的整數）表示的烯基）（專利文獻4：日本專利4221300號公報） （5）剝離塗料組成物，含有烯基官能化聚矽氧烷、氫化矽官能化聚矽氧烷、及鉑族金屬，烯基官能化聚矽氧烷使用磷腈鹼觸媒製作。（專利文獻5：日本專利特表2009-513740號公報） 但是，所述專利文獻4及專利文獻5中記載的組成物如下所述硬化不充分。Therefore, a method of forming a peelable film with a small amount of platinum is required. For example, Patent Document 4 and Patent Document 5 describe the following compositions. (4) Silicone compositions comprising polyorganosiloxanes having at least two alkenyl groups bonded to silicon atoms per molecule, hydrogenated organosiloxanes having SiH groups at the terminals and side chains, and MD Vi Q resin and hydrosilation inhibitor for adjusting the system (in the above, M is R 3 SiO 1/2 , D Vi is RPSiO 2/2 , Q is SiO 4/2 , and R is independently without fat An unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms in a family unsaturated bond, and P is an alkenyl group represented by -(CH 2 ) n -CH=CH 2 (n is an integer of 0 to 6). ) (Patent Document 4: Japanese Patent No. 4221300) (5) Release coating composition containing alkenyl-functional polysiloxane, hydridosilicon-functional polysiloxane, platinum group metal, and alkenyl-functional polysiloxane Oxane is produced using a phosphazene base catalyst. (Patent Document 5: Japanese Patent Application Laid-Open No. 2009-513740) However, the compositions described in Patent Document 4 and Patent Document 5 are insufficiently cured as described below.
例如，專利文獻4記載的組成物的特徵在於使用反應性良好的末端SiH基、及皮膜形成性MDVi Q樹脂，在實施例中，以60 ppm的鉑濃度，在150℃下對組成物加熱1.8秒來進行硬化，但未記載以60 ppm以下的鉑量進行硬化的方法。另外，以鉑濃度60 ppm硬化的硬化皮膜中的提取成分（未反應的矽氧烷的量）多達5.8%～6.5%，大量存在未硬化的矽氧烷，硬化不充分。另外，專利文獻4並無關於剝離特性的記載。For example, the composition described in Patent Document 4 is characterized in that a terminal SiH group with good reactivity and a film-forming MD Vi Q resin are used. In the example, the composition was heated at 150° C. at a platinum concentration of 60 ppm. The hardening is performed in 1.8 seconds, but the method of hardening with a platinum amount of 60 ppm or less is not described. In addition, the extracted component (the amount of unreacted siloxane) in the cured film cured at a platinum concentration of 60 ppm was as high as 5.8% to 6.5%, and uncured siloxane was present in a large amount, resulting in insufficient curing. In addition, Patent Document 4 does not describe peeling properties.
專利文獻5中記載的組成物的特徵在於，烯基官能化聚矽氧烷是具有MDQ單元的分支矽氧烷。記載了藉由具有末端乙烯基的分支鏈提高了製作交聯皮膜的概率。在專利文獻5記載的實施例中，利用磷腈觸媒使四-二甲基乙烯基矽氧基矽烷反應，合成含烯基的分支矽氧烷，接著，以鉑濃度為40 ppm的量調配氫化矽官能化聚矽氧烷及鉑觸媒，在100℃15秒及115℃20秒的條件下，使組成物硬化。專利文獻5中，關於該組成物的硬化狀態，利用甲基異丁基酮提取硬化物進行了評價。提取的未反應矽氧烷的比例為6.4%～25.2%，均較多，硬化不充分。另外，未進行剝離特性等其他評價。 [現有技術文獻] [專利文獻]The composition described in Patent Document 5 is characterized in that the alkenyl-functional polysiloxane is a branched siloxane having an MDQ unit. It is described that the probability of forming a cross-linked film is improved by the branched chain having a terminal vinyl group. In the example described in Patent Document 5, tetra-dimethylvinylsiloxysilane was reacted with a phosphazene catalyst to synthesize an alkenyl group-containing branched siloxane, which was then prepared at a platinum concentration of 40 ppm. The hydride functionalized polysiloxane and platinum catalyst were used to cure the composition at 100°C for 15 seconds and 115°C for 20 seconds. In Patent Document 5, the cured state of the composition was evaluated by extracting the cured product with methyl isobutyl ketone. The ratio of the extracted unreacted siloxane was 6.4% to 25.2%, which were large, and the hardening was insufficient. In addition, other evaluations, such as peeling characteristics, were not performed. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開昭47-32072號公報 [專利文獻2]日本專利特公昭35-13709號公報 [專利文獻3]日本專利特開昭54-162787號公報 [專利文獻4]日本專利4221300號公報 [專利文獻5]日本專利特表2009-513740號公報[Patent Document 1] Japanese Patent Laid-Open No. 47-32072 [Patent Document 2] Japanese Patent Publication No. 35-13709 [Patent Document 3] Japanese Patent Laid-Open No. 54-162787 [Patent Document 4] Japanese Patent No. 4221300 [Patent Document 5] Japanese Patent Publication No. 2009-513740
[發明所欲解決之課題][The problem to be solved by the invention]
在硬化充分進行的皮膜中，一般而言，未反應矽氧烷的提取量至少為5%以下，較佳為3%以下。如所述專利文獻4及專利文獻5所述，硬化皮膜中存在5%以上的未反應矽氧烷時，矽氧烷轉移到膠的表面，殘留接著率大幅降低。另外，由於殘存SiH基殘留得多，因此與充分硬化的情況相比，剝離力變高。因此，需要能夠以少的鉑觸媒量進行硬化的有機聚矽氧烷組成物，但尚不知道在鉑濃度60質量ppm以下獲得充分的硬化皮膜的加成反應硬化型有機聚矽氧烷組成物。In the film in which the hardening has progressed sufficiently, generally, the extraction amount of unreacted siloxane is at least 5% or less, preferably 3% or less. As described in Patent Document 4 and Patent Document 5, when 5% or more of unreacted siloxane is present in the cured film, the siloxane is transferred to the surface of the glue, and the residual adhesion rate is greatly reduced. In addition, since a large amount of residual SiH groups remain, the peeling force becomes higher than that in the case of sufficiently hardening. Therefore, there is a need for an organopolysiloxane composition that can be cured with a small amount of platinum catalyst, but the composition of an addition reaction-curable organopolysiloxane that can obtain a sufficient cured film at a platinum concentration of 60 mass ppm or less has not been known thing.
本發明是鑒於所述情況而成者，其目的在於提供一種加成反應硬化型有機聚矽氧烷組成物，即使是少的鉑族金屬系觸媒量，亦可充分硬化而發揮良好的密接性，形成具有與先前同等的剝離力的硬化皮膜，並且，在含有觸媒毒成分的基材中加成反應硬化亦充分進行，適於提供矽酮橡膠、剝離紙或剝離膜用的剝離皮膜。 [解決課題之手段]The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide an addition reaction hardening type organopolysiloxane composition which can be sufficiently hardened to exhibit good adhesion even with a small amount of platinum group metal-based catalyst. It can form a hardened film with the same peeling force as the previous one, and the addition reaction hardening is also fully progressed in the base material containing the catalyst poison. It is suitable for providing silicone rubber, release paper or release film for release film. . [Means of Solving Problems]
本發明者等人進行了努力研究，發現藉由在加成反應硬化型有機聚矽氧烷組成物中，含烯基的有機聚矽氧烷在一分子中具有兩個以上矽原子鍵結烯基，且平均具有0.01～2.9個(甲基)丙烯酸基，可解決所述課題，從而完成本發明。The present inventors have made diligent studies and found that in the addition reaction hardening type organopolysiloxane composition, the alkenyl group-containing organopolysiloxane has two or more silicon atom-bonded alkenes in one molecule. The present invention can be solved by solving the above-mentioned problems and having an average of 0.01 to 2.9 (meth)acrylic groups.
即，本發明提供含有下述（A）成分～（C）成分的加成反應硬化型有機聚矽氧烷組成物。 （A）一分子中具有兩個以上矽原子鍵結烯基，且平均具有0.01～2.9個(甲基)丙烯酸基的有機聚矽氧烷 （B）一分子中具有兩個以上矽原子鍵結氫原子（Si-H基）的有機氫聚矽氧烷：所述（B）成分中的Si-H基的個數相對於所述（A）成分中的烯基的個數之比為1～5的量，及 （C）鉑族金屬系觸媒：相對於所述組成物的總質量，鉑族金屬含量為1質量ppm～100質量ppm的量 [發明的效果]That is, the present invention provides an addition reaction curable organopolysiloxane composition containing the following (A) components to (C) components. (A) Organopolysiloxane having two or more silicon atoms-bonded alkenyl groups in one molecule and having an average of 0.01 to 2.9 (meth)acrylic groups (B) Organohydrogen polysiloxane having two or more silicon atom-bonded hydrogen atoms (Si-H groups) in one molecule: the number of Si-H groups in the (B) component is relative to the (B) A) an amount in which the ratio of the number of alkenyl groups in the component is 1 to 5, and (C) Platinum group metal-based catalyst: an amount in which the platinum group metal content is 1 to 100 ppm by mass relative to the total mass of the composition [Effect of invention]
本發明的有機聚矽氧烷組成物雖然鉑族金屬系觸媒量少，但充分硬化，而能夠形成具有與先前的加成型組成物同等的剝離力的硬化皮膜。本發明的有機聚矽氧烷組成物即使在以往難以硬化的條件下亦可硬化，且由於鉑族金屬觸媒量少，而能夠大幅降低製造成本。另外，對於含有觸媒毒的基材亦可藉由加成反應進行硬化。The organopolysiloxane composition of the present invention has a small amount of platinum group metal catalyst, but is sufficiently cured to form a cured film having a peeling force equivalent to that of the conventional addition-type composition. The organopolysiloxane composition of the present invention can be hardened even under conditions that have been difficult to harden in the past, and since the amount of the platinum group metal catalyst is small, the production cost can be greatly reduced. In addition, the substrate containing catalyst poison can also be hardened by addition reaction.
以下，對本發明進行詳細說明。 [（A）成分] （A）成分的特徵在於，一分子中具有兩個以上、較佳為2～50個矽原子鍵結烯基，平均具有0.01～2.9個、較佳為0.03～2.7個、更佳為0.05～2.5個(甲基)丙烯酸基。該有機聚矽氧烷可為先前公知者，可單獨為一種或者適當組合兩種以上。藉由含烯基的有機聚矽氧烷在所述範圍內具有(甲基)丙烯酸基，即使觸媒量少亦可良好地硬化。（A）成分例如可藉由下述平均式（1）表示。 [化1] (R3 SiO1/2 )a (R2 PSiO1/2 )b (R2 ASiO1/2 )c (R2 SiO2/2 )d (RPSiO2/2 )e (RASiO2/2 )f (RSiO3/2 )g (PSiO3/2 )h (ASiO3/2 )i (SiO4/2 )j （1） 式（1）中，R彼此獨立地為不具有脂肪族不飽和鍵的碳原子數1～12的未經取代或經取代的一價烴基，P為由-(CH2 )n -CH=CH2 （n為0或0～6的正數）表示的烯基，A為由CH2 =CR2 COR3 -表示的含(甲基)丙烯酸基的基，R2 為氫原子或甲基，R3 為OR4 或R4 的2價基，R4 為碳原子數1～20的2價有機基，可具有分支或環狀結構，亦可包含環氧基、酯鍵、胺基甲酸酯鍵、醚鍵、異氰酸酯鍵、或羥基。a、b、c、e、h、i及f彼此獨立地為0或正數。b、e及n不會同時為0，且2≦b+e+h≦300。d為50～4,000的正數，g為0或0～50的正數，j為0或0～50的正數，c、f及i不會同時為0，且0.01≦c+f+i≦2.9。較佳為0.03≦c+f+i≦2.7，更佳為0.05≦c+f+i≦2.5。Hereinafter, the present invention will be described in detail. [Component (A)] The component (A) has two or more, preferably 2 to 50 silicon atom-bonded alkenyl groups in one molecule, and has an average of 0.01 to 2.9, preferably 0.03 to 2.7 , more preferably 0.05 to 2.5 (meth)acrylic groups. The organopolysiloxane may be known in the past, and may be used alone or in an appropriate combination of two or more. Since the alkenyl group-containing organopolysiloxane has a (meth)acrylic group within the above-mentioned range, even if the amount of the catalyst is small, it can be cured favorably. (A) Component can be represented by the following average formula (1), for example. [Chemical 1] (R 3 SiO 1/2 ) a (R 2 PSiO 1/2 ) b (R 2 ASiO 1/2 ) c (R 2 SiO 2/2 ) d (RPSiO 2/2 ) e (RASiO 2 /2 ) f (RSiO 3/2 ) g (PSiO 3/2 ) h (ASiO 3/2 ) i (SiO 4/2 ) j (1) In formula (1), R independently of each other does not have aliphatic An unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms in an unsaturated bond, and P is an alkene represented by -(CH 2 ) n -CH=CH 2 (n is 0 or a positive number from 0 to 6) group, A is a (meth)acrylic group-containing group represented by CH 2 =CR 2 COR 3 -, R 2 is a hydrogen atom or a methyl group, R 3 is OR 4 or a divalent group of R 4 , R 4 is The divalent organic group having 1 to 20 carbon atoms may have a branched or cyclic structure, and may contain an epoxy group, an ester bond, a urethane bond, an ether bond, an isocyanate bond, or a hydroxyl group. a, b, c, e, h, i and f independently of each other are 0 or a positive number. b, e and n are not 0 at the same time, and 2≦b+e+h≦300. d is a positive number from 50 to 4,000, g is 0 or a positive number from 0 to 50, j is 0 or a positive number from 0 to 50, c, f and i cannot be 0 at the same time, and 0.01≦c+f+i≦2.9. Preferably, it is 0.03≦c+f+i≦2.7, more preferably 0.05≦c+f+i≦2.5.
所述式（1）中，R彼此獨立地為不具有脂肪族不飽和鍵的碳原子數1～12的、未經取代或經取代的一價烴基，較佳為碳原子數1～10，更佳為碳原子數1～8。更詳細而言，可列舉甲基、乙基、丙基、丁基、戊基、己基、辛基、癸基、十二烷基等烷基；環己基等環烷基；苯基、萘基、甲苯基等芳基；苄基、苯乙基等芳烷基；該些基的與碳原子鍵結的氫原子的一部分被鹵素原子、環氧基、胺基、聚醚基、氰基、羥基等取代而得者。該些中，就硬化性、降低所獲得的硬化物的剝離力的觀點而言，較佳為R的總數的80莫耳%以上為甲基。In the formula (1), R independently of each other is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms without aliphatic unsaturated bonds, preferably 1 to 10 carbon atoms, More preferably, it has 1-8 carbon atoms. More specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl; cycloalkyl groups such as cyclohexyl; phenyl and naphthyl , aryl groups such as tolyl groups; aralkyl groups such as benzyl and phenethyl groups; a part of the hydrogen atoms bonded to carbon atoms in these groups are replaced by halogen atoms, epoxy groups, amine groups, polyether groups, cyano groups, Hydroxyl and other substitutions derived. Among these, it is preferable that 80 mol% or more of the total number of R is a methyl group from the viewpoint of curability and reduction of the peeling force of the obtained cured product.
P是由-(CH2 )n -CH=CH2 （n是0～6的整數）表示的烯基。例如可列舉乙烯基、烯丙基、丁烯基、丙烯基、5-己烯基、辛烯基、及癸烯基等，其中較佳為乙烯基。P is an alkenyl group represented by -(CH 2 ) n -CH=CH 2 (n is an integer of 0 to 6). For example, a vinyl group, an allyl group, a butenyl group, a propenyl group, a 5-hexenyl group, an octenyl group, a decenyl group, etc. are mentioned, and among them, a vinyl group is preferable.
A是由CH2 =CR2 COR3 -表示的含(甲基)丙烯酸基的基。R2 為氫原子或甲基，較佳為氫原子。R3 是OR4 或R4 所表示的2價基，R4 是碳原子數1～20的2價有機基，可具有分支或環狀結構，可含有環氧基、酯鍵、胺基甲酸酯鍵、醚鍵、異氰酸酯鍵、及羥基。作為R4 ，例如可例示亞甲基、伸乙基、伸丙基、伸丁基、六亞甲基、八亞甲基及伸癸基等直鏈狀的伸烷基；甲基伸乙基、甲基伸丙基等分支狀伸烷基；伸環己基等環狀伸烷基；伸丙烯基等伸烯基；伸苯基等伸芳基；亞甲基伸苯基、及亞甲基伸苯基亞甲基等伸芳烷基等二價烴基。可在該二價烴基中***酯鍵、胺基甲酸酯鍵、醚鍵、及異氰酸酯鍵，亦可將該些組合使用。進而，該些二價烴基的氫原子的一部分或全部可經環氧基或羥基取代。該些中，作為R4 ，較佳為伸丙基。A is a (meth)acrylic group-containing group represented by CH 2 =CR 2 COR 3 —. R 2 is a hydrogen atom or a methyl group, preferably a hydrogen atom. R 3 is a divalent group represented by OR 4 or R 4 , R 4 is a divalent organic group with 1 to 20 carbon atoms, may have a branched or cyclic structure, and may contain an epoxy group, an ester bond, an aminomethyl group ester bond, ether bond, isocyanate bond, and hydroxyl group. Examples of R 4 include linear alkylene groups such as methylene, ethylidene, propylidene, butylene, hexamethylene, octamethylene, and decylene; methyl ethylidene , branched alkylene such as methyl propylidene; cyclic alkylene such as cyclohexylene; alkenylene such as propenylene; aryl such as phenylene; methylene phenylene, and methylene Divalent hydrocarbon groups such as phenylene methylene and other aralkyl groups. An ester bond, a urethane bond, an ether bond, and an isocyanate bond may be inserted into the divalent hydrocarbon group, and these may be used in combination. Furthermore, a part or all of hydrogen atoms of these divalent hydrocarbon groups may be substituted with epoxy groups or hydroxyl groups. Among these, as R 4 , a propylidene group is preferable.
式（1）中的a、b、c、e、及h彼此獨立地為0或正數。b、e、h不會同時為0，且2≦b+e+h≦300，較佳為2≦b+e+h≦10，進而佳的範圍為2≦b+e+h≦4。a較佳為0或1～4的正數。特別是，烯基較佳為與M單元或D單元的矽原子鍵結，b較佳為1～6的正數，a+b較佳為2～10的正數。e較佳為0或1～10的正數，h較佳為0或1～5的正數。a, b, c, e, and h in the formula (1) are independently 0 or a positive number. b, e, and h are not 0 at the same time, and 2≦b+e+h≦300, preferably 2≦b+e+h≦10, and more preferably 2≦b+e+h≦4. a is preferably 0 or a positive number of 1-4. In particular, the alkenyl group is preferably bonded to the silicon atom of the M unit or the D unit, b is preferably a positive number of 1-6, and a+b is preferably a positive number of 2-10. e is preferably 0 or a positive number of 1-10, and h is preferably 0 or a positive number of 1-5.
式（1）中的c、f、及i彼此獨立地為0或正數。c、f、及i不會同時為0，較佳的範圍為0.01≦c+f+i≦2.9。較佳為0.03≦c+f+i≦2.7，更佳為0.05≦c+f+i≦2.5。特別是(甲基)丙烯酸基較佳為與D單元的矽原子鍵結，c及i較佳為0，f較佳為0.01～2.9的正數。c, f, and i in the formula (1) are independently 0 or a positive number. c, f, and i are not all 0 at the same time, and the preferred range is 0.01≦c+f+i≦2.9. Preferably, it is 0.03≦c+f+i≦2.7, more preferably 0.05≦c+f+i≦2.5. In particular, the (meth)acrylic group is preferably bonded to the silicon atom of the D unit, c and i are preferably 0, and f is preferably a positive number of 0.01 to 2.9.
式（1）中，表示R2 SiO2/2 單元的數量的d是50～4,000的正數，較佳為60～1,000的正數，進而佳為70～300的正數。d小於所述下限值時，若塗敷速度為200 m/min以上，則煙霧產生量增大，有機聚矽氧烷組成物的塗敷表面有可能粗糙。另外，d超過所述上限值時，有機聚矽氧烷組成物的動態黏度變得過高，塗敷性降低，因此平滑性變差，塗敷量的差有可能因位置而變大。In formula (1), d representing the number of R 2 SiO 2/2 units is a positive number of 50 to 4,000, preferably a positive number of 60 to 1,000, and more preferably a positive number of 70 to 300. When d is less than the lower limit, when the coating speed is 200 m/min or more, the amount of smoke generated increases, and the coating surface of the organopolysiloxane composition may be rough. In addition, when d exceeds the upper limit, the dynamic viscosity of the organopolysiloxane composition becomes too high, and the coating property is lowered, so that the smoothness is deteriorated, and the difference in the coating amount may increase depending on the position.
式（1）中表示RSiO3/2 單元的數量的g為0或0～50的正數，較佳為0或0～10的正數，更佳為0或0～5的正數。表示SiO4/2 單元的數量的j為0或0～50的正數，較佳為0或0～10的正數，更佳為0或0～5的正數。In formula (1), g representing the number of RSiO 3/2 units is 0 or a positive number of 0-50, preferably 0 or a positive number of 0-10, more preferably 0 or a positive number of 0-5. j representing the number of SiO 4/2 units is 0 or a positive number from 0 to 50, preferably 0 or a positive number from 0 to 10, more preferably 0 or a positive number from 0 to 5.
（A）成分較佳為具有乙烯值0.0001 mol/100 g～0.7 mol/100 g，更佳為0.005 mol/100 g～0.5 mol/100 g，進而佳為0.01 mol/100 g～0.3 mol/100 g。乙烯值低於所述下限值時，反應點變得過少，有時會引起硬化不良。乙烯值超過所述上限值時，交聯密度變得過高，低速剝離力變得過高，有時變得不易剝離。The component (A) preferably has an ethylene value of 0.0001 mol/100 g to 0.7 mol/100 g, more preferably 0.005 mol/100 g to 0.5 mol/100 g, still more preferably 0.01 mol/100 g to 0.3 mol/100 g. When the ethylene value is lower than the lower limit, the number of reaction points becomes too small, which may cause poor curing. When the ethylene value exceeds the upper limit, the crosslinking density becomes too high, the low-speed peeling force becomes too high, and the peeling becomes difficult in some cases.
（A）成分宜較佳為具有重量平均分子量3,000～30萬，較佳為5,000～10萬，進而佳為7,000～3萬，特佳為9,000～2萬。（A）成分的重量平均分子量低於所述下限值時，有時向基材的塗敷量變得不充分。另外，超過所述上限值時，有時作業性降低。再者，本發明中，重量平均分子量例如可藉由29 Si-核磁共振（nuclear magnetic resonance，NMR）測定（測定溶媒：氘代氯仿）、或基於凝膠滲透層析（gel permeation chromatography，GPC）分析（溶媒：甲苯）而得出的聚苯乙烯換算的重量平均分子量來測定（以下相同）。The component (A) preferably has a weight average molecular weight of 3,000 to 300,000, more preferably 5,000 to 100,000, more preferably 7,000 to 30,000, and particularly preferably 9,000 to 20,000. When the weight-average molecular weight of the component (A) is less than the lower limit, the coating amount to the base material may become insufficient. Moreover, when the said upper limit value is exceeded, workability|operativity may fall. Furthermore, in the present invention, the weight average molecular weight can be measured by, for example, 29 Si-nuclear magnetic resonance (NMR) (measurement solvent: deuterated chloroform), or based on gel permeation chromatography (GPC) The weight average molecular weight in terms of polystyrene obtained by analysis (solvent: toluene) was measured (the same applies hereinafter).
（A）成分較佳為具有利用旋轉黏度計而測定的25℃下的黏度10 mPa·s以上，且具有30質量%甲苯溶解黏度（在甲苯中溶解30質量%有機聚矽氧烷而得的溶液的黏度）70,000 mPa·s以下，更佳為具有50 mPa·s以上且30質量%甲苯溶解黏度60,000 mPa·s以下。黏度小於10 mPa·s時，塗敷量有可能變得不充分。另外，超過30質量%甲苯溶解黏度70,000 mPa·s時，作業性有可能降低。The component (A) preferably has a viscosity at 25° C. measured by a rotational viscometer of 10 mPa·s or more, and has a toluene dissolution viscosity of 30% by mass (a product obtained by dissolving 30% by mass of organopolysiloxane in toluene). The viscosity of the solution) is 70,000 mPa·s or less, more preferably 50 mPa·s or more and a 30 mass % toluene solution viscosity of 60,000 mPa·s or less. When the viscosity is less than 10 mPa·s, the coating amount may become insufficient. In addition, when it exceeds 30 mass % of toluene solution viscosity 70,000 mPa·s, workability may fall.
本發明的（A）有機聚矽氧烷中，烯基及(甲基)丙烯酸基的鍵結部位可為分子鏈末端及側鏈中的任意一個，但(甲基)丙烯酸基較佳為位於側鏈，特別是宜直接或經由烴而鍵結在D單元的矽原子上。特佳為(甲基)丙烯酸基只位於側鏈。烯基較佳為與M單元或D單元的矽原子鍵結。作為所述（A）成分，例如可列舉：兩末端含有烯基且側鏈含有(甲基)丙烯酸基的矽氧烷、側鏈含有烯基且側鏈含有(甲基)丙烯酸基的矽氧烷、單末端及側鏈含有烯基且側鏈含有(甲基)丙烯酸基的矽氧烷、兩末端及側鏈含有烯基且側鏈含有(甲基)丙烯酸基的矽氧烷、及分支型末端含有烯基且側鏈含有(甲基)丙烯酸基的矽氧烷。In the (A) organopolysiloxane of the present invention, the bonding site of the alkenyl group and the (meth)acrylic group may be any one of the molecular chain terminal and the side chain, but the (meth)acrylic group is preferably located in The side chains, in particular, are preferably bonded to the silicon atom of the D unit, either directly or via a hydrocarbon. It is especially preferable that the (meth)acrylic group is located only in the side chain. The alkenyl group is preferably bonded to the silicon atom of the M unit or the D unit. As said (A) component, the siloxane which contains an alkenyl group at both ends and contains a (meth)acryl group in a side chain, and the siloxane which contains an alkenyl group in the side chain and contains a (meth)acryl group in the side chain, for example, can be mentioned. Alkane, siloxane containing alkenyl at one end and side chain and (meth)acrylic group in side chain, siloxane containing alkenyl at both ends and side chain and containing (meth)acrylic group in side chain, and branch Siloxane containing an alkenyl group at the end and a (meth)acrylic group in the side chain.
更詳細而言，可列舉下述結構的矽氧烷。 MVi 2 Dd DA f 、 M2 Dd DVi e DA f 、 MVi 3 Dd DA f T1 、 MVi 4 De DA f T2 、 MVi 2 Dd DVi e DA f 、 MVi 2 Dd DVi e DA f Q1 、 MA 2 Dd DVi e DA f 、及 MA 2 M1 Dd DVi e DA f T1 等。 進而詳細地說，可列舉下述結構的矽氧烷。 MVi 2 D100 DA 0.01 、 MVi 2 D150 DA 0.05 、 MVi 2 D200 DA 0.1 、 MVi 2 D300 DA 2.5 、 MVi 3 D200 DA 0.1 、及 MVi 2 D200 DA 0.5 Q1 等。 在所述說明中，M為R3 SiO1/2 、MVi 為R2 PSiO1/2 、D為R2 SiO2/2 、DVi 為RPSiO2/2 、DA 為RASiO2/2 、T為RSiO3/2 、Q為SiO4/2 。R、A及P如上所述。More specifically, the siloxane of the following structure is mentioned. M Vi 2 D d D A f , M 2 D d D Vi e D A f , M Vi 3 D d D A f T 1 , M Vi 4 D e D A f T 2 , M Vi 2 D d D Vi e D A f , M Vi 2 D d D Vi e D A f Q 1 , M A 2 D d D Vi e D A f , and M A 2 M 1 D d D Vi e D A f T 1 and the like. More specifically, siloxanes of the following structures can be mentioned. M Vi 2 D 100 D A 0.01 , M Vi 2 D 150 D A 0.05 , M Vi 2 D 200 D A 0.1 , M Vi 2 D 300 D A 2.5 , M Vi 3 D 200 D A 0.1 , and M Vi 2 D 200 D A 0.5 Q 1 etc. In the above description, M is R 3 SiO 1/2 , M Vi is R 2 PSiO 1/2 , D is R 2 SiO 2/2 , D Vi is RPSiO 2/2 , D A is RASiO 2/2 , T is RSiO 3/2 and Q is SiO 4/2 . R, A and P are as described above.
[（B）成分] （B）成分為一分子中具有兩個以上矽原子鍵結氫原子（Si-H基）且不具有(甲基)丙烯酸基的有機氫聚矽氧烷，可單獨使用一種或適當組合兩種以上使用。藉由該有機氫聚矽氧烷的Si-H基與（A）成分的烯基發生加成反應，形成有機聚矽氧烷交聯物。[(B) Ingredient] (B) Component is an organohydrogen polysiloxane having two or more silicon atoms-bonded hydrogen atoms (Si-H groups) in one molecule and no (meth)acrylic group, which can be used alone or in an appropriate combination of two. Use above. The organopolysiloxane cross-linked product is formed by the addition reaction between the Si-H group of the organohydrogenpolysiloxane and the alkenyl group of the component (A).
（B）成分較佳為在一分子中具有3～100個矽原子鍵結氫原子（Si-H基），更佳為具有10～100個。另外，Si-H基含量較佳為0.001莫耳/100 g～3.5莫耳/100 g，更佳為0.01莫耳/100 g～2.5莫耳/100 g，進而佳為0.02莫耳/100 g～2.0莫耳/100 g。Si-H基含量過少時，組成物的硬化性或密接性有可能變差。過多時，剝離力有時會變重。The component (B) preferably has 3 to 100 silicon atom-bonded hydrogen atoms (Si—H groups) in one molecule, and more preferably has 10 to 100 atoms. In addition, the Si-H group content is preferably 0.001 mol/100 g to 3.5 mol/100 g, more preferably 0.01 mol/100 g to 2.5 mol/100 g, further preferably 0.02 mol/100 g ~2.0 moles/100 g. When the Si—H group content is too small, there is a possibility that the sclerosing property and the adhesiveness of the composition may deteriorate. When too much, peeling force may become heavy.
作為（B）有機氫聚矽氧烷，較佳為藉由下述式（2）表示。 [化2] (R'3 SiO1/2 )m (R'2 HSiO1/2 )n (R'2 SiO2/2 )o (R'HSiO2/2 )p (R'SiO3/2 )q (HSiO3/2 )r (SiO4/2 )s （2） 式（2）中，R'是彼此獨立地不具有脂肪族不飽和鍵的、碳原子數1～12的未經取代或經取代的一價烴基。m、n、o、及q彼此獨立地為0或正數，p為0～100的正數，r為0～10的正數，s為0～10的正數，n、p、r不會同時為0，且2≦n+p+r≦100。The (B) organohydrogen polysiloxane is preferably represented by the following formula (2). [Chem. 2] (R' 3 SiO 1/2 ) m (R' 2 HSiO 1/2 ) n (R' 2 SiO 2/2 ) o (R'HSiO 2/2 ) p (R' SiO 3/2 ) q (HSiO 3/2 ) r (SiO 4/2 ) s (2) In formula (2), R' is an unsubstituted C 1 to 12 unsubstituted group independently of each other that does not have an aliphatic unsaturated bond or a substituted monovalent hydrocarbon group. m, n, o, and q are independently 0 or a positive number, p is a positive number from 0 to 100, r is a positive number from 0 to 10, s is a positive number from 0 to 10, and n, p, and r are never 0 at the same time. , and 2≦n+p+r≦100.
所述式（2）中，R'彼此獨立地為不具有脂肪族不飽和鍵的、碳原子數1～12的未經取代或經取代的一價烴基，較佳為碳原子數1～10，更佳為碳原子數1～8。例如可列舉：甲基、乙基、丙基、丁基、戊基、己基、辛基、癸基、及十二烷基等烷基；環己基等環烷基；苯基、萘基、甲苯基等芳基；苄基、苯乙基等芳烷基；該些基的與碳原子鍵結的氫原子的一部分被鹵素原子、環氧基、胺基、聚醚基、氰基、羥基等取代而得者。其中，就硬化性、降低所獲得的硬化物的剝離力的觀點而言，較佳為R'的總數的80莫耳%以上為甲基。In the above formula (2), R' independently of each other is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and having no aliphatic unsaturated bond, preferably 1 to 10 carbon atoms. , more preferably 1 to 8 carbon atoms. For example, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl; cycloalkyl groups such as cyclohexyl; phenyl, naphthyl, and toluene Aryl groups such as benzyl and phenethyl groups; aralkyl groups such as benzyl and phenethyl groups; a part of hydrogen atoms bonded to carbon atoms in these groups are replaced by halogen atoms, epoxy groups, amine groups, polyether groups, cyano groups, hydroxyl groups, etc. Replaced by. Among them, it is preferable that 80 mol% or more of the total number of R' is a methyl group from the viewpoint of curability and reduction of the peeling force of the obtained cured product.
式（2）中，m、n、o、及q彼此獨立地為0或正數，m較佳為0或1～10的正數，n較佳為0或1～10的正數，m+n較佳為2～12的正數。o較佳為0或1～100的正數，q較佳為0或1～10的正數。另外，p為0～100的正數，較佳為2～100的正數，更佳為10～80的正數。r為0～10的正數，較佳為0或1～5的正數，s為0～10的正數，較佳為0或1～5的正數。另外，n、p、r不會同時為0，n+p+r為3～100的正數，較佳為10～80的正數。In formula (2), m, n, o, and q are independently 0 or a positive number, m is preferably 0 or a positive number from 1 to 10, n is preferably 0 or a positive number from 1 to 10, and m+n is more A positive number from 2 to 12 is preferred. o is preferably 0 or a positive number from 1 to 100, and q is preferably 0 or a positive number from 1 to 10. Moreover, p is a positive number of 0-100, Preferably it is a positive number of 2-100, More preferably, it is a positive number of 10-80. r is a positive number from 0 to 10, preferably 0 or a positive number from 1 to 5, and s is a positive number from 0 to 10, preferably 0 or a positive number from 1 to 5. In addition, n, p, and r are not 0 at the same time, and n+p+r is a positive number from 3 to 100, preferably a positive number from 10 to 80.
作為（B）有機氫聚矽氧烷，例如可列舉兩末端含有氫矽烷基的矽氧烷、側鏈含有氫矽烷基的矽氧烷、單末端及側鏈含有氫矽烷基的矽氧烷、兩末端及側鏈含有氫矽烷基的矽氧烷等。As (B) organohydrogen polysiloxane, for example, siloxane containing a hydrosilyl group at both ends, a siloxane containing a hydrosilyl group in a side chain, a siloxane containing a hydrosilyl group at one end and a side chain, Siloxanes containing hydrosilyl groups at both ends and side chains, etc.
更詳細地說，可列舉下述結構的有機氫聚矽氧烷。 MH 2 Do 、M2 DH p 、 M2 Do DH p 、 MH 2 Do DH p 、 MH 3 Do T1 、 MH 4 Do T2 、及 Mm Do DH p TH r 等。 更詳細地說，可列舉下述結構的有機氫聚矽氧烷。 MH 2 D10 、 MH 2 D100 、 M2 DH 80 、 M2 D27 DH 3 、 M2 D97 DH 3 、 M2 D26 DH 4 、 M2 D25 DH 5 、 M2 D24 DH 6 、 M2 D96 DH 4 、 M2 D95 DH 5 、 MH 3 D100 T1 、 MH 4 D100 T2 、 MH 2 D97 DH 1 、 MH 2 D95 DH 3 、 M3 D93 DH 3 TH 1 、 M2 DH 30 、M2 DH 60 等。 在所述各式中，M為R'3 SiO1/2 、MH 為R'2 HSiO1/2 、D為R'2 SiO2/2 、DH 為R'HSiO2/2 、T為R'SiO3/2 、TH 為HSiO3/2 。R'如上所述。More specifically, organohydrogenpolysiloxanes of the following structures can be mentioned. M H 2 D o , M 2 D H p , M 2 D o D H p , M H 2 D o D H p , M H 3 D o T 1 , M H 4 D o T 2 , and M m D o DHpTHr et al . More specifically, organohydrogenpolysiloxanes of the following structures can be mentioned. M H 2 D 10 , M H 2 D 100 , M 2 D H 80 , M 2 D 27 D H 3 , M 2 D 97 D H 3 , M 2 D 26 D H 4 , M 2 D 25 D H 5 , M 2 D 24 D H 6 , M 2 D 96 D H 4 , M 2 D 95 D H 5 , M H 3 D 100 T 1 , M H 4 D 100 T 2 , M H 2 D 97 D H 1 , M H 2 D 95 D H 3 , M 3 D 93 D H 3 T H 1 , M 2 D H 30 , M 2 D H 60 and the like. In the above formulas, M is R' 3 SiO 1/2 , M H is R' 2 HSiO 1/2 , D is R' 2 SiO 2/2 , DH is R'HSiO 2/2 , and T is R'SiO 3/2 and TH are HSiO 3/2 . R' is as described above.
（B）成分宜較佳為具有重量平均分子量194～10,000，更佳為具有874～5,000。若重量平均分子量低於所述下限值，則組成物的密接性有時會大幅惡化。若重量平均分子量超過所述上限值，則反應性變差，硬化性降低，可能會觀察到殘留接著率降低或硬化不足引起的剝離力上升。The component (B) preferably has a weight average molecular weight of 194 to 10,000, more preferably 874 to 5,000. When the weight average molecular weight is less than the lower limit value, the adhesiveness of the composition may be significantly deteriorated. When the weight average molecular weight exceeds the upper limit, the reactivity is deteriorated, the curability is decreased, and the peeling force due to a decrease in the residual adhesion rate or insufficient curing may be observed.
（B）成分的藉由奧士華（Ostwald）型黏度計測定的25℃下的動態黏度較佳為2 mm2 /s～500 mm2 /s，更佳為2 mm2 /s～300 mm2 /s，進而佳為5 mm2 /s～200 mm2 /s。25℃下的動態黏度小於2 mm2 /s時，由於分子量小，因此反應性好，但與基材的密接性有時會惡化。另外，超過500 mm2 /s時，反應性變差，固化性降低，有時會觀察到殘留接著率降低、或固化不足引起的剝離力上升。The dynamic viscosity at 25°C of the component (B) measured by an Ostwald viscometer is preferably 2 mm 2 /s to 500 mm 2 /s, more preferably 2 mm 2 /s to 300 mm 2 /s, more preferably 5 mm 2 /s to 200 mm 2 /s. When the dynamic viscosity at 25°C is less than 2 mm 2 /s, the molecular weight is small, so the reactivity is good, but the adhesion to the substrate may be deteriorated. On the other hand, when it exceeds 500 mm 2 /s, the reactivity is deteriorated, the curability is deteriorated, the residual adhesion rate is decreased, or the peeling force due to insufficient curing may be observed.
關於（B）成分的調配量，（B）成分中的Si-H基的個數相對於（A）成分中的烯基的個數之比為1～5，較佳為相當於1.2～3的量。（B）成分過少時，組成物的硬化性與密接性不充分。過多時，殘存的Si-H基量增加，因此剝離力增高，Si-H基隨著時間經過而減少，因此剝離力隨時間經過而變化大。About the compounding quantity of (B) component, the ratio of the number of objects of Si-H group in (B) component to the number of objects of alkenyl group in (A) component is 1-5, Preferably it corresponds to 1.2-3 amount. When the component (B) is too small, the curability and adhesiveness of the composition are insufficient. When it is too large, the amount of the remaining Si—H groups increases, so that the peeling force increases, and the Si—H groups decrease with the passage of time, so the peeling force changes greatly with the passage of time.
[（C）成分] （C）鉑族金屬系觸媒可使用作為加成反應觸媒使用的公知的觸媒。作為該鉑族金屬系觸媒，例如可列舉鉑系、鈀系、銠系、及釕系等觸媒。其中特佳為鉑系觸媒。作為鉑系觸媒，例如可列舉：鉑二氧化矽-氧化鋁、鉑氧化鋁-鹵素、鉑銠等鉑系化合物、鉑與乙烯基矽氧烷等的錯合物、氯鉑酸的醇溶液或醛溶液、氯鉑酸與各種烯烴類的錯鹽、氯鉑酸與乙烯基矽氧烷等的錯合物等。[(C) Ingredient] (C) As the platinum group metal-based catalyst, a known catalyst used as an addition reaction catalyst can be used. Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Among them, the particularly preferred is a platinum-based catalyst. Examples of platinum-based catalysts include platinum-silica-alumina, platinum-alumina-halogen, platinum-based compounds such as platinum-rhodium, complexes of platinum and vinylsiloxane, and alcohol solutions of chloroplatinic acid. Or aldehyde solution, chloroplatinic acid and various alkenes, complexes of chloroplatinic acid and vinylsiloxane, etc.
（C）成分的調配量為觸媒量，用於提供剝離紙或剝離膜用的硬化皮膜的鉑族金屬濃度通常在有機聚矽氧烷組成物中為60質量ppm～500質量ppm。與此相對，本發明中的鉑族金屬系觸媒的調配量相對於組成物的總質量以鉑族金屬質量換算計為1質量ppm～100質量ppm。較佳為3質量ppm～60質量ppm，進而佳為5質量ppm～40質量ppm，最佳為10質量ppm～30質量ppm。關於本發明的有機聚矽氧烷組成物，如所述般即使鉑族金屬觸媒量少，亦充分硬化，而能夠提供具有良好物性的硬化皮膜。觸媒量低於所述下限值時，加成反應不進行，未反應的官能基殘留得多，因此無法形成充分的硬化皮膜。另外，若超過所述上限值，有時會與水分或控制劑發生反應，或可使用時間變短，在作業中硬化。(C) The compounding quantity of a component is a catalyst quantity, and the platinum group metal density|concentration for providing the cured film for release paper or a release film is 60 mass ppm - 500 mass ppm normally in an organopolysiloxane composition. On the other hand, the compounding quantity of the platinum group metal catalyst in this invention is 1 mass ppm - 100 mass ppm in conversion of platinum group metal mass with respect to the total mass of a composition. Preferably it is 3 mass ppm - 60 mass ppm, More preferably, it is 5 mass ppm - 40 mass ppm, Most preferably, it is 10 mass ppm - 30 mass ppm. As described above, the organopolysiloxane composition of the present invention is sufficiently cured even if the amount of the platinum group metal catalyst is small, and a cured film having favorable physical properties can be provided. When the catalyst amount is less than the lower limit, the addition reaction does not proceed, and many unreacted functional groups remain, so that a sufficient cured film cannot be formed. Moreover, if it exceeds the said upper limit, it may react with water|moisture content or a control agent, or the usable time may become short, and it may harden|cure during operation.
[（D）成分] 本發明的有機聚矽氧烷組成物視需要亦可含有（D）加成反應控制劑。加成反應控制劑控制鉑族金屬系觸媒的觸媒活性，可為以往公知的控制劑。例如可列舉有機氮化合物、有機磷化合物、乙炔系化合物、肟化合物、以及有機氯化合物等。更詳細而言，可列舉1-乙炔基-1-環己醇、3-甲基-1-丁炔-3-醇、3,5-二甲基-1-己炔-3-醇、3-甲基-1-戊炔-3-醇、2-苯基-3-丁炔-2-醇等乙炔系醇；3-甲基-3-戊烯-1-炔、3,5-二甲基-3-己烯-1-炔等乙炔系化合物；1,1-二甲基丙炔基氧基三甲基矽烷等乙炔系化合物與烷氧基矽烷或矽氧烷或氫矽烷的反應產物、四甲基乙烯基矽氧烷環狀體等乙烯基矽氧烷、苯並***等有機氮化合物及其他有機磷化合物、肟化合物、馬來酸二烯丙基等馬來酸化合物、有機氯化合物等。[(D)ingredients] The organopolysiloxane composition of this invention may contain (D) an addition reaction control agent as needed. The addition reaction control agent controls the catalytic activity of the platinum group metal-based catalyst, and may be a conventionally known control agent. For example, an organic nitrogen compound, an organic phosphorus compound, an acetylene type compound, an oxime compound, an organic chlorine compound, etc. are mentioned. More specifically, 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3 - Ethynyl alcohols such as methyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol; 3-methyl-3-penten-1-yne, 3,5-diol Acetylene compounds such as methyl-3-hexen-1-yne; reaction of acetylene compounds such as 1,1-dimethylpropynyloxytrimethylsilane with alkoxysilane, siloxane or hydrosilane Products, vinylsiloxanes such as tetramethylvinylsiloxane rings, organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds, oxime compounds, maleic acid compounds such as diallyl maleate, Organochlorine compounds, etc.
（D）成分的調配量相對於（A）成分100質量份較佳為0.01質量份～5質量份，更佳為0.1質量份～3質量份。藉由在該範圍內調配，可良好地控制加成硬化反應。調配時，若過少，則可使用時間變短，作業中可能會引起硬化，若過多，則不進行加成反應，因此可能無法形成硬化皮膜。0.01-5 mass parts is preferable with respect to 100 mass parts of (A) components, and, as for the compounding quantity of (D) component, 0.1-3 mass parts is more preferable. By adjusting within this range, the addition hardening reaction can be well controlled. When blending, if it is too small, the usable time will be shortened, and hardening may occur during operation, and if it is too large, the addition reaction will not proceed, so that a hardened film may not be formed.
[其他成分] 在本發明的有機聚矽氧烷組成物中，除了所述（A）～（D）成分以外，亦可在不損害本發明效果的範圍內調配以往的剝離紙或剝離膜用加成反應硬化型組成物中調配的其他成分。例如，可列舉有機溶劑、及以賦予滑動性為目的的（A）～（C）成分以外的高分子量直鏈型有機聚矽氧烷、以調節剝離力為目的的（A）～（C）成分以外的具有芳基的矽酮樹脂、矽酮樹脂（resin）、二氧化矽等。[other ingredients] In the organopolysiloxane composition of the present invention, in addition to the components (A) to (D) described above, conventional release papers or release films may be prepared by addition reaction curing within a range that does not impair the effects of the present invention. other ingredients formulated in the type composition. For example, organic solvents and high-molecular-weight linear organopolysiloxanes other than components (A) to (C) for the purpose of imparting sliding properties, and (A) to (C) for the purpose of adjusting the peeling force can be mentioned. Other than the ingredients, there are silicone resins, silicone resins (resin), silica, etc. which have aromatic groups.
作為有機溶劑，較佳使用甲苯、己烷、二甲苯、甲基乙基酮（別名：2-丁酮）等可溶於有機聚矽氧烷的有機溶劑（不含矽氧烷溶劑）；八甲基四矽氧烷、十甲基五矽氧烷等低黏度的環狀矽氧烷、M2 Dt （M、D與所述式（1）相同。t為0～200，較佳為1-50的數。）等直鏈矽氧烷；M2+u Dt Tu （M、D、T與所述式（1）相同。t為0～200，較佳為1～50，u為1～10，較佳為1～3。）等支鏈矽氧烷等有機聚矽氧烷（矽氧烷溶劑）。As the organic solvent, organic solvents soluble in organopolysiloxane such as toluene, hexane, xylene, and methyl ethyl ketone (alias: 2-butanone) are preferably used (excluding siloxane solvents); Low-viscosity cyclic siloxanes such as methyltetrasiloxane and decamethylpentasiloxane, M 2 D t (M, D are the same as the formula (1). t is 0-200, preferably 1-50.) and other linear siloxanes; M 2+u D t Tu (M, D, T are the same as the formula (1). t is 0-200, preferably 1-50, u is 1 to 10, preferably 1 to 3.) Organopolysiloxane (siloxane solvent) such as branched chain siloxane.
有機溶劑的量較佳為（A）成分與（B）成分的合計質量的3～50倍，更佳為8～30倍。The amount of the organic solvent is preferably 3 to 50 times the total mass of the (A) component and (B) component, more preferably 8 to 30 times the mass.
本發明的有機聚矽氧烷組成物藉由混合所述（A）～（C）成分及視需要的（D）成分或任意成分各者的規定量而獲得。所獲得的有機聚矽氧烷組成物較佳為具有由奧士華型黏度計測定的25℃下的動態黏度10 mm2 /s～2000 mm2 /s，更佳為具有15 mm2 /s～1000 mm2 /s。The organopolysiloxane composition of the present invention is obtained by mixing the above-mentioned (A) to (C) components and optionally (D) components or predetermined amounts of each of the optional components. The obtained organopolysiloxane composition preferably has a dynamic viscosity at 25°C of 10 mm 2 /s to 2000 mm 2 /s, more preferably 15 mm 2 /s, as measured by an Oswald viscometer. ~1000 mm 2 /s.
本發明的有機聚矽氧烷組成物藉由塗敷在各種基材上並硬化來提供剝離紙及剝離膜等。例如，藉由塗敷輥（三輥、五輥、凹版輥、平版凹版輥等）塗佈在紙、塑膠膜等片狀基材上後，藉由常規方法進行加熱硬化，從而在片狀基材的單面形成矽酮硬化皮膜，從而獲得剝離紙及剝離片等。The organopolysiloxane composition of the present invention provides release paper, release film, and the like by coating and curing on various substrates. For example, after applying a coating roll (three rolls, five rolls, gravure rolls, lithographic gravure rolls, etc.) to sheet-like substrates such as paper and plastic films, it is heated and hardened by conventional methods, so that the sheet-like substrates can be hardened by heating. A silicone hardened film is formed on one side of the material to obtain a release paper and a release sheet.
作為紙基材，例如可列舉玻璃紙、聚乙烯層壓紙、聚乙烯醇樹脂塗佈紙、黏土塗佈紙等。作為塑膠膜基材，例如可列舉聚乙烯、聚丙烯、聚對苯二甲酸乙二酯等聚酯等膜。As a paper base material, cellophane, polyethylene laminated paper, polyvinyl alcohol resin-coated paper, clay-coated paper, etc. are mentioned, for example. Examples of the plastic film base material include films such as polyethylene, polypropylene, and polyester such as polyethylene terephthalate.
有機聚矽氧烷組成物向基材的塗佈量只要是足以在片狀基材表面形成矽酮硬化皮膜的量即可，例如為0.1 g/m2 ～5.0 g/m2 左右。過多量的塗佈有時反而會導致剝離性能的降低。加熱硬化條件根據基材的種類或塗佈量而不同，但可藉由在80℃～200℃、較佳為100℃～180℃下加熱1～60秒、較佳為2～30秒而在基材上形成硬化皮膜。 [實施例]The coating amount of the organopolysiloxane composition to the substrate may be an amount sufficient to form a silicone cured film on the surface of the sheet-like substrate, for example, about 0.1 g/m 2 to 5.0 g/m 2 . Too much coating may actually lead to a decrease in peeling performance. The heat-hardening conditions vary depending on the type of the substrate and the coating amount, but can be cured by heating at 80°C to 200°C, preferably 100°C to 180°C for 1 to 60 seconds, preferably 2 to 30 seconds. A hardened film is formed on the substrate. [Example]
以下示出實施例及比較例，更詳細地說明本發明，但本發明不限於下述實施例。 再者，下述列舉的重量平均分子量藉由29 Si-NMR（測定溶媒：氘代氯仿）求出，黏度為在25℃下使用旋轉黏度計測定的值（mPa·s），動態黏度均為在25℃下使用奧華士型黏度計測定的值（mm2 /s）。Hereinafter, the present invention will be described in more detail by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the weight-average molecular weights listed below were obtained by 29 Si-NMR (measurement solvent: deuterated chloroform), the viscosities were values (mPa·s) measured using a rotational viscometer at 25°C, and the dynamic viscosities were all Value (mm 2 /s) measured using an Ovas-type viscometer at 25°C.
實施例及比較例中使用的各成分如下。 （A）成分 在下述中，M為R3 SiO1/2 、MVi 為R2 PSiO1/2 、D為R2 SiO2/2 、DVi 為RPSiO2/2 、DA 為RASiO2/2 、T為RSiO3/2 。R為甲基，P為乙烯基。 1）由下述平均式表示的、一分子中具有兩個乙烯基、且平均具有0.05個丙烯酸基的甲基聚矽氧烷（1） MVi 2 D150 DA 0.05 式中A為CH2 =CHCO(CH2 )3 -，乙烯值為0.0177莫耳/100 g，黏度為413 mPa·s。重量平均分子量為11294.6。 2）由下述平均式表示的、一分子中具有兩個乙烯基、平均具有0.1個丙烯酸基的甲基聚矽氧烷（2） MVi 2 D150 DA 0.1 式中A為CH2 =CHCO(CH2 )3 -，乙烯值為0.0177莫耳/100 g，黏度為415 mPa·s。重量平均分子量為11303.2。 3）由下述平均式表示的、一分子中具有兩個乙烯基、平均具有2.5個丙烯酸基的甲基聚矽氧烷（3） MVi 2 D220 DA 2.5 式中A為CH2 =CHCO(CH2 )3 -，乙烯值為0.0118莫耳/100 g，黏度為1082 mPa·s。重量平均分子量為16896。 4）由下述平均式表示的、一分子中具有兩個乙烯基、平均具有1個丙烯酸基的甲基聚矽氧烷（4） MVi 3 D150 DA 1 T1 式中A為CH2 =CHCO(CH2 )3 -，乙烯值為0.0258莫耳/100 g，黏度為258 mPa·s。重量平均分子量為11618。 5）由下述平均式表示的、側鏈具有2個乙烯基，平均具有0.1個丙烯酸基的甲基聚矽氧烷（5） M2 DVi 2 D148 DA 0.1 式中A為CH2 =CHCO(CH2 )3 -，乙烯值為0.0174莫耳/100 g，黏度為418 mPa·s。重量平均分子量為11303.2。 6）由下述平均式表示的、一分子中具有兩個乙烯基、平均具有0.1個甲基丙烯酸基的甲基聚矽氧烷（6） MVi 2 D150 DA' 0.1 式中A'為CH2 =C(CH3 )CO(CH2 )3 -，乙烯值為0.0177莫耳/100 g，黏度為416 mPa·s。重量平均分子量為11304.6。Each component used in an Example and a comparative example is as follows. Component (A) In the following, M is R 3 SiO 1/2 , M Vi is R 2 PSiO 1/2 , D is R 2 SiO 2/2 , D Vi is RPSiO 2/2 , and D A is RASiO 2/ 2. T is RSiO 3/2 . R is methyl and P is vinyl. 1) Methylpolysiloxane having two vinyl groups in one molecule and having an average of 0.05 acrylic groups represented by the following average formula (1) M Vi 2 D 150 D A 0.05 where A is CH 2 =CHCO(CH 2 ) 3 -, the ethylene value is 0.0177 mol/100 g, and the viscosity is 413 mPa·s. The weight average molecular weight was 11294.6. 2) Methylpolysiloxane having two vinyl groups in one molecule and having an average of 0.1 acrylic groups represented by the following average formula (2) M Vi 2 D 150 D A 0.1 where A is CH 2 = CHCO(CH 2 ) 3 -, the ethylene value is 0.0177 mol/100 g, and the viscosity is 415 mPa·s. The weight average molecular weight was 11303.2. 3) Methylpolysiloxane having two vinyl groups in one molecule and having an average of 2.5 acrylic groups represented by the following average formula (3) M Vi 2 D 220 D A 2.5 where A is CH 2 = CHCO(CH 2 ) 3 -, the ethylene value is 0.0118 mol/100 g, and the viscosity is 1082 mPa·s. The weight average molecular weight was 16,896. 4) Methylpolysiloxane having two vinyl groups in one molecule and one acrylic group on average represented by the following average formula (4) M Vi 3 D 150 D A 1 T 1 wherein A is CH 2 =CHCO(CH 2 ) 3 -, the ethylene value is 0.0258 mol/100 g, and the viscosity is 258 mPa·s. The weight average molecular weight was 11618. 5) Methylpolysiloxane having 2 vinyl groups in the side chain and 0.1 acrylic group in average represented by the following average formula (5) M 2 D Vi 2 D 148 D A 0.1 where A is CH 2 =CHCO(CH 2 ) 3 -, the ethylene value is 0.0174 mol/100 g, and the viscosity is 418 mPa·s. The weight average molecular weight was 11303.2. 6) Methylpolysiloxane represented by the following average formula, having two vinyl groups in one molecule and having an average of 0.1 methacrylate groups (6) M Vi 2 D 150 D A' 0.1 where A' It is CH 2 =C(CH 3 )CO(CH 2 ) 3 -, the ethylene value is 0.0177 mol/100 g, and the viscosity is 416 mPa·s. The weight average molecular weight was 11304.6.
（B）成分 由下述平均式表示的甲基氫聚矽氧烷（7） M2 DH 100 在所述中，M為R'3 SiO1/2 ，DH 為R'HSiO2/2 。R'為甲基，分子鏈兩末端具有三甲基矽氧基。Si-H基含量為1.62 mol/100 g，動態黏度為35 mm2 /s。重量平均分子量為6162。(B) Methylhydrogenpolysiloxane (7) M 2 DH 100 represented by the following average formula as the component, wherein M is R' 3 SiO 1/2 and DH is R'HSiO 2/2 . R' is a methyl group, and both ends of the molecular chain have trimethylsiloxy groups. The Si-H group content was 1.62 mol/100 g, and the dynamic viscosity was 35 mm 2 /s. The weight average molecular weight was 6162.
其他添加成分（比較例） 1）由下述平均式表示的、兩末端具有乙烯基、不具有(甲基)丙烯酸基的甲基聚矽氧烷（8） MVi 2 D150 式中MVi 為R2 PSiO1/2 ，D為R2 SiO2/2 ，R為甲基，P為CH2 =CH-，乙烯值為0.0177 mol/100 g，黏度為405 mPa·s。重量平均分子量為11286。 2）由下述平均式表示的、一分子中具有兩個乙烯基、平均具有10個丙烯酸基的甲基聚矽氧烷（9） MVi 2 D150 DA 10 式中的MVi 為R2 PSiO1/2 ，D為R2 SiO2/2 ，DA 為RASiO2/2 ，R為甲基，A為CH2 =CHCO(CH2 )3 -，P為CH2 =CH-，乙烯值為0.0154 莫耳/100 g，黏度為427 mPa·s。重量平均分子量為13006。 3）由下述平均式表示的、兩末端具有丙烯酸基的甲基聚矽氧烷（10） MA 2 D5 式中的MA 為R2 ASiO1/2 、D為R2 SiO2/2 、R為甲基、A為CH2 =CHCO(CH2 )3 -、黏度為7 mPa·s。重量平均分子量為728。Other additives (comparative example) 1) Methylpolysiloxane (8) represented by the following average formula, having vinyl groups at both ends and not having (meth)acrylic groups MVi 2 D150 where MVi for R2 PSiO1/2 , D is R2 SiO2/2 , R is methyl, P is CH2 =CH-, the ethylene value is 0.0177 mol/100 g, and the viscosity is 405 mPa·s. The weight average molecular weight was 11286. 2) Methylpolysiloxane having two vinyl groups in one molecule and an average of 10 acrylic groups represented by the following average formula (9) MVi 2 D150 DA 10 M in the formulaVi for R2 PSiO1/2 , D is R2 SiO2/2 , DA for RASiO2/2 , R is methyl, A is CH2 =CHCO(CH2 )3 -, P is CH2 =CH-, the ethylene value is 0.0154 mol/100 g, and the viscosity is 427 mPa·s. The weight average molecular weight was 13,006. 3) Methylpolysiloxane (10) having acrylic groups at both ends represented by the following average formula MA 2 D5 M in the formulaA for R2 ASiO1/2 , D is R2 SiO2/2 , R is methyl, A is CH2 =CHCO(CH2 )3 -, the viscosity is 7 mPa·s. The weight average molecular weight was 728.
[實施例1] 按照下述表1記載的配方混合各成分來製備加成反應硬化型有機聚矽氧烷組成物。 即，加入（A）所述甲基聚矽氧烷（1）100質量份、（B）所述甲基氫聚矽氧烷（7）1.97質量份、及（D）1-乙炔基-1-環己醇0.3質量份，攪拌至均勻後，按照相對於組成物的總質量以鉑原子質量換算計成為20質量ppm的量加入（C）鉑與乙烯基矽氧烷的錯合物，攪拌至均勻。所獲得的生成物是具有動態黏度393 mm2 /s的有機聚矽氧烷組成物。H/Vi（（B）成分中的Si-H基的個數相對於（A）成分中的烯基的個數的比（以下相同））為1.8。[Example 1] The respective components were mixed according to the formulation described in Table 1 below to prepare an addition reaction-curable organopolysiloxane composition. That is, (A) 100 parts by mass of the methylpolysiloxane (1), (B) 1.97 parts by mass of the methylhydrogenpolysiloxane (7), and (D) 1-ethynyl-1 were added -0.3 parts by mass of cyclohexanol, after stirring until uniform, (C) a complex of platinum and vinylsiloxane was added in an amount of 20 mass ppm in terms of platinum atomic mass relative to the total mass of the composition, and stirred to uniform. The obtained product was an organopolysiloxane composition having a dynamic viscosity of 393 mm 2 /s. H/Vi (the ratio of the number of Si—H groups in the component (B) to the number of alkenyl groups in the component (A) (the same applies hereinafter)) was 1.8.
[實施例2] 如下述表1所示，除了作為（A）成分使用100質量份所述甲基聚矽氧烷（2）以外，重覆實施例1，獲得具有動態黏度395 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Example 2] As shown in Table 1 below, except that 100 parts by mass of the methylpolysiloxane (2) was used as the component (A), Example 1 was repeated to obtain a dynamic viscosity of 395 mm 2 /s. , H/Vi=1.8 organopolysiloxane composition.
[實施例3] 如下述表1所示，除了作為（A）成分使用100質量份所述甲基聚矽氧烷（3）、作為（B）成分使用1.97質量份所述甲基氫聚矽氧烷（7）以外，重覆實施例1，獲得具有動態黏度為1035 mm2 /s，H/Vi=1.8的有機聚矽氧烷組成物。[Example 3] As shown in Table 1 below, except that 100 parts by mass of the methyl polysiloxane (3) was used as the component (A) and 1.97 parts by mass of the methyl hydrogen polysilicon was used as the component (B) Except for the oxane (7), Example 1 was repeated to obtain an organopolysiloxane composition having a dynamic viscosity of 1035 mm 2 /s and H/Vi=1.8.
[實施例4] 如下述表1所示，除了作為（A）成分使用100質量份所述甲基聚矽氧烷（4）、作為（B）成分使用2.87質量份所述甲基氫聚矽氧烷（7）以外，重覆實施例1，獲得具有動態黏度244 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Example 4] As shown in Table 1 below, except that 100 parts by mass of the methylpolysiloxane (4) was used as the component (A) and 2.87 parts by mass of the methylhydrogenpolysilicon was used as the component (B) Except for the oxane (7), Example 1 was repeated to obtain an organopolysiloxane composition having a dynamic viscosity of 244 mm 2 /s and H/Vi=1.8.
[實施例5] 如下述表1所示，除了作為（A）成分使用100質量份所述甲基聚矽氧烷（5）、作為（B）成分使用1.639質量份所述甲基氫聚矽氧烷（7）以外，重覆實施例1，獲得具有動態黏度398 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Example 5] As shown in Table 1 below, except that 100 parts by mass of the methyl polysiloxane (5) was used as the component (A) and 1.639 parts by mass of the methyl hydrogen polysilicon was used as the component (B) Except for the oxane (7), Example 1 was repeated to obtain an organopolysiloxane composition having a dynamic viscosity of 398 mm 2 /s and H/Vi=1.8.
[實施例6] 如下述表1所示，除了作為（A）成分使用50質量份所述甲基聚矽氧烷（3）及50質量份所述甲基聚矽氧烷（8），作為（B）成分使用1.51質量份所述甲基氫聚矽氧烷（7）之外，重覆實施例1，製備具有動態黏度646 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Example 6] As shown in Table 1 below, except that 50 parts by mass of the methylpolysiloxane (3) and 50 parts by mass of the methylpolysiloxane (8) were used as the component (A), Example 1 was repeated except that 1.51 parts by mass of the methylhydrogenpolysiloxane (7) was used as the component (B) to prepare an organopolysiloxane having a dynamic viscosity of 646 mm 2 /s and H/Vi=1.8 composition.
[實施例7] 如下述表1所示，除了作為（A）成分使用100質量份所述甲基聚矽氧烷（6）以外，重覆實施例1，製備了具有動態黏度396 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Example 7] As shown in Table 1 below, except that 100 parts by mass of the methylpolysiloxane (6) was used as the component (A), Example 1 was repeated to prepare a product having a dynamic viscosity of 396 mm 2 / s, H/Vi=1.8 organopolysiloxane composition.
[實施例8] 如下述表1所示，除了使用相對於組成物的總質量以鉑原子質量換算計為15質量ppm的（C）鉑與乙烯基矽氧烷的錯合物以外，重覆實施例1，獲得具有動態黏度395 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Example 8] As shown in Table 1 below, except that the complex compound of (C) platinum and vinylsiloxane was used at 15 ppm by mass in terms of platinum atomic mass with respect to the total mass of the composition, the procedure was repeated. In Example 1, an organopolysiloxane composition with a dynamic viscosity of 395 mm 2 /s and H/Vi=1.8 was obtained.
[比較例1] 如下述表1所述，除了使用100質量份所述兩末端含有乙烯基的甲基聚矽氧烷（8）代替所述（A）成分以外，重覆實施例1，獲得具有動態黏度386 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Comparative Example 1] As shown in Table 1 below, except that 100 parts by mass of the methylpolysiloxane (8) containing vinyl groups at both ends was used instead of the component (A), Example 1 was repeated to obtain Organopolysiloxane composition with a dynamic viscosity of 386 mm 2 /s and H/Vi=1.8.
[比較例2] 如下述表2所述，除了使用100質量份兩末端含有乙烯基且側鏈含有丙烯酸基的甲基聚矽氧烷（9）代替所述（A）成分，將所述（B）甲基氫聚矽氧烷（7）的量設為1.71質量份以外，重覆實施例1，獲得具有動態黏度408 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Comparative Example 2] As described in Table 2 below, except that 100 parts by mass of methylpolysiloxane (9) containing vinyl groups at both ends and acrylic groups in side chains was used instead of the (A) component, the (A) B) Except that the amount of methylhydrogenpolysiloxane (7) was set to 1.71 parts by mass, Example 1 was repeated to obtain an organopolysiloxane composition having a dynamic viscosity of 408 mm 2 /s and H/Vi=1.8 .
[比較例3] 如下述表2所述，除了在所述比較例1的組成中進一步添加1質量份在兩末端具有丙烯酸基的有機聚矽氧烷MA 2 D5 （10）以外，重覆比較例1，獲得具有動態黏度388 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Comparative Example 3] As shown in Table 2 below, except that 1 part by mass of the organopolysiloxane M A 2 D 5 (10) having acrylic groups at both ends was further added to the composition of Comparative Example 1, the same amount of weight was added. Covering Comparative Example 1, an organopolysiloxane composition with a dynamic viscosity of 388 mm 2 /s and H/Vi=1.8 was obtained.
[比較例4] 如下述表2所述，除了在所述比較例1的組成中進一步加入丙烯酸（11）1質量份以外，重覆比較例1，獲得具有動態黏度393 mm2 /s、H/Vi=1.8的有機聚矽氧烷組成物。[Comparative Example 4] As described in Table 2 below, except that 1 part by mass of acrylic acid (11) was further added to the composition of Comparative Example 1, Comparative Example 1 was repeated to obtain a dynamic viscosity of 393 mm 2 /s, H Organopolysiloxane composition with /Vi=1.8.
[參考例1] 如下述表2所述，與比較例1相同地加入兩末端含有乙烯基的甲基聚矽氧烷（8）100質量份、（B）甲基氫聚矽氧烷（7）1.97質量份（H/Vi=1.8）、作為（D）成分的1-乙炔基-1-環己醇0.3質量份，攪拌均勻後，按照相對於組成物的總質量以鉑原子質量換算計成為100質量ppm的方式加入（C）鉑與乙烯基矽氧烷的錯合物，攪拌至均勻。 所獲得的生成物是具有動態黏度387 mm2 /s的有機聚矽氧烷組成物。[Reference Example 1] As described in Table 2 below, 100 parts by mass of methylpolysiloxane (8) containing vinyl groups at both ends, (B) methylhydrogenpolysiloxane (7) were added in the same manner as in Comparative Example 1. ) 1.97 parts by mass (H/Vi=1.8), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol as the component (D), after stirring uniformly, calculated in terms of platinum atomic mass relative to the total mass of the composition (C) The complex of platinum and vinylsiloxane was added so that it might become 100 mass ppm, and it stirred until uniform. The obtained product was an organopolysiloxane composition having a dynamic viscosity of 387 mm 2 /s.
對所述獲得的各有機聚矽氧烷組成物進行了下述所示的各評價。將結果示於表1～表4。Each of the evaluations shown below was performed on each of the organopolysiloxane compositions obtained above. The results are shown in Tables 1 to 4.
〔剝離力〕 將有機聚矽氧烷組成物塗佈在RI測試機（IHI機械系統股份有限公司製造）的金屬輥上，使兩根輥旋轉45秒鐘，均勻地拉伸。之後，將組成物自橡膠輥轉印至玻璃紙ASP（奧斯龍明士克（Ahlstrom-munksjo）公司製造，含有觸媒毒）。將轉印有組成物的玻璃紙在120℃的熱風式乾燥機中加熱30秒鐘，獲得具有厚度0.9 g/m2 ～1.1 g/m2 的硬化皮膜的剝離紙。在該狀態下，在25℃下老化24小時後，在該剝離紙的硬化皮膜表面（自橡膠輥轉印的一面側）貼合TESA-7475膠帶（特莎英國股份有限公司（tesa UK Ltd）），切斷成2.5 cm×18 cm的大小。將其夾在玻璃板中，在25℃、70 g/cm2 的載荷下、以及70℃、20 g/cm2 的載荷下、於室溫下老化24小時。老化後，剝離該試驗片的一端，將膠帶的基材端部以0.3 m/min的剝離速度向相對於玻璃紙為180度的角度方向拉伸。此時，使用拉伸試驗機（島津製作所股份有限公司AGS-50G型）測定剝離膠帶所需的力（即「剝離力」）（N/25mm）。[Peeling Force] The organopolysiloxane composition was applied to a metal roll of an RI tester (manufactured by IHI Machine Systems Co., Ltd.), and the two rolls were rotated for 45 seconds to stretch uniformly. After that, the composition was transferred from a rubber roll to cellophane ASP (manufactured by Ahlstrom-munksjo, containing catalytic poison). The cellophane on which the composition was transferred was heated in a hot air dryer at 120° C. for 30 seconds to obtain a release paper having a cured film having a thickness of 0.9 g/m 2 to 1.1 g/m 2 . In this state, after aging at 25°C for 24 hours, TESA-7475 tape (tesa UK Ltd) was attached to the hardened film surface of the release paper (one side transferred from the rubber roll). ), cut into a size of 2.5 cm × 18 cm. It was sandwiched in a glass plate and aged at room temperature for 24 hours at 25°C under a load of 70 g/cm 2 and at 70° C. under a load of 20 g/cm 2 . After aging, one end of the test piece was peeled off, and the end of the base material of the tape was pulled in an angular direction of 180 degrees with respect to the cellophane at a peeling speed of 0.3 m/min. At this time, the force required to peel off the tape (that is, "peel force") (N/25mm) was measured using a tensile tester (AGS-50G, Shimadzu Corporation).
〔殘留接著率〕 將所述剝離力測定後的TESA-7475膠帶貼合在聚酯膜上，使2 kg的輥往返一次來施加荷重。放置30分鐘後，剝離TESA-7475膠帶的一端，將其端部向相對於聚酯膜成180度的角度的方向拉伸。測定以剝離速度0.3 m/min剝離膠帶時所需的力（以下稱為「剝離力A」，為N/25 mm）。 作為坯料，在聚酯膜上貼上未使用的TESA-7475膠帶，與所述相同地，使2 kg的輥往返一次來施加荷重。放置30分鐘後，剝離TESA-7475膠帶的一端，將其端部向相對於聚酯膜成180度角度的方向拉伸。測定以剝離速度0.3 m/min剝離膠帶時所需的力（以下稱為「剝離力B」，為N/25 mm）。 藉由（剝離力A的值）/（剝離力B的值）×100求出殘留接著率（%）。[Residual adhesion rate] The TESA-7475 tape after the measurement of the peeling force was attached to the polyester film, and a 2 kg roller was reciprocated once to apply a load. After being left to stand for 30 minutes, one end of the TESA-7475 tape was peeled off, and the end portion was stretched in a direction at an angle of 180 degrees with respect to the polyester film. The force required to peel off the tape at a peeling speed of 0.3 m/min (hereinafter referred to as "peeling force A", N/25 mm) was measured. As a blank, unused TESA-7475 tape was stuck on the polyester film, and a 2 kg roller was reciprocated once to apply a load in the same manner as described above. After standing for 30 minutes, one end of the TESA-7475 tape was peeled off, and the end was stretched in a direction of 180 degrees with respect to the polyester film. The force required to peel off the tape at a peeling speed of 0.3 m/min (hereinafter referred to as "peeling force B", N/25 mm) was measured. The residual adhesion rate (%) was obtained by (value of peeling force A)/(value of peeling force B)×100.
〔硬化性〕 將各有機聚矽氧烷組成物塗佈在測試機的金屬輥上。使包括金屬輥與橡膠輥的兩根輥接觸旋轉45秒，均勻地拉伸有機聚矽氧烷組成物後，自橡膠輥向韓國製玻璃紙轉印組成物。將轉印有有機聚矽氧烷組成物的聚乙烯層壓紙在120℃的熱風式乾燥機中加熱30秒鐘，獲得具有厚度0.9 g/m2 ～1.1 g/m2 的硬化皮膜的剝離紙。自乾燥機中取出該剝離紙，立即用食指用力擦拭硬化皮膜面10次，塗佈紅色魔法油墨（Magic ink），觀察油墨的濃度或硬化皮膜狀態。 基於以下指標對結果進行評價，並示於表2～表4。 ·指痕看起來深的情況為「×」 ·指痕看起來淺的情況為「△」 ·幾乎看不到指痕的情況為「○」[Curability] Each organopolysiloxane composition was coated on a metal roll of a testing machine. Two rolls including a metal roll and a rubber roll were rotated in contact for 45 seconds, and the organopolysiloxane composition was uniformly stretched, and then the composition was transferred from the rubber roll to the Korean-made cellophane. The polyethylene laminate paper to which the organopolysiloxane composition was transferred was heated in a hot air dryer at 120° C. for 30 seconds to obtain peeling of a cured film having a thickness of 0.9 g/m 2 to 1.1 g/m 2 Paper. Take out the release paper from the dryer, immediately wipe the hardened film surface 10 times vigorously with the index finger, apply a red magic ink (Magic ink), and observe the concentration of the ink or the state of the hardened film. The results were evaluated based on the following indexes, and are shown in Tables 2 to 4.・The case where the finger marks appear to be deep is indicated by “×” ・The case where the finger marks appear shallow is indicated by “△” ・The case where the finger marks are hardly visible is indicated by “○”
與剝離力測定的情況同樣地在玻璃紙表面形成的有機聚矽氧烷組成物的硬化皮膜的表面重疊厚度36 μm的聚對苯二甲酸乙二酯膜，在室溫下、0.98 MPa的加壓下壓接20小時後，將聚對苯二甲酸乙二酯膜自硬化皮膜取下。在該聚對苯二甲酸乙二酯膜的與硬化皮膜接觸的表面，塗佈油性的油墨（商品名：魔法油墨（Magic ink）、寺西化學工業股份有限公司製造），根據其排斥情況，評價矽酮遷移性。 基於以下指標對結果進行評價，示於表2～表4。 無油墨的排斥（矽酮無遷移性或相當少）為「○」 有油墨的排斥（矽酮的遷移性多）為「×」As in the case of the peel force measurement, a polyethylene terephthalate film with a thickness of 36 μm was superimposed on the surface of the cured film of the organopolysiloxane composition formed on the surface of the cellophane, and a pressure of 0.98 MPa was applied at room temperature. After 20 hours of lower pressure bonding, the polyethylene terephthalate film was removed from the self-curing film. On the surface of the polyethylene terephthalate film in contact with the cured film, an oily ink (trade name: Magic ink, manufactured by Terai Chemical Industry Co., Ltd.) was applied, and evaluation was made based on the repellency. Silicone mobility. The results were evaluated based on the following indexes, and are shown in Tables 2 to 4. Rejection without ink (silicon has no migration or fairly little) is "○" Repulsion of ink (more migration of silicone) is "×"
[密接性] 藉由與所述硬化性的評價方法相同的方法將有機聚矽氧烷組成物轉印到玻璃紙上，在120℃的熱風式乾燥機中加熱30秒鐘，獲得剝離紙。將該剝離紙在60℃90%RH的恆溫恆濕機中保存1天後，藉由與硬化性同樣的方法，用食指用力擦拭硬化皮膜面10次，塗佈紅色魔法油墨，觀察油墨的濃度或硬化皮膜狀態。 基於以下指標對結果進行評價，示於表2～表4。 ·指痕看起來深的情況為「×」 ·指痕看起來淺的情況為「△」 ·幾乎看不到指痕的情況為「○」[adhesion] The organopolysiloxane composition was transcribe|transferred on the cellophane by the same method as the evaluation method of the said hardenability, and it heated for 30 second in a 120 degreeC hot air dryer, and obtained the release paper. After the release paper was stored in a constant temperature and humidity machine at 60°C and 90%RH for 1 day, the hardened film surface was vigorously wiped 10 times with the index finger in the same manner as for hardening, and the red magic ink was applied, and the concentration of the ink was observed. or hardened film state. The results were evaluated based on the following indexes, and are shown in Tables 2 to 4. ・If the finger marks look deep, "×" ・When the finger marks appear to be light, "△" ・If the finger marks are hardly visible, "○"
[表1]
[表2]
如所述表1所示，參考例1是先前的加成反應硬化型有機聚矽氧烷組成物，（C）觸媒的鉑濃度多達100質量ppm。由於該組成物的硬化反應充分進行，因此硬化性、矽酮遷移性及密接性良好，剝離力低，殘留接著率高，具有良好的剝離特性。 比較例1是在該參考例1的組成中，將（C）觸媒的鉑濃度設為20質量ppm的組成。此種情況下，在120℃×30秒的加熱處理中，有機聚矽氧烷組成物不硬化，成為油狀。即，硬化不充分。另外，在25℃下老化1天後，硬化亦不充分，擦拭塗敷面後，指痕清晰。而且由於遷移量多，硬化性及矽酮遷移性差。As shown in Table 1, Reference Example 1 is a conventional addition reaction hardening type organopolysiloxane composition, and the platinum concentration of the catalyst (C) is as high as 100 mass ppm. Since the hardening reaction of this composition proceeds sufficiently, the hardening property, silicone migration property, and adhesiveness are good, the peeling force is low, the residual adhesion rate is high, and the peeling property is favorable. In Comparative Example 1, in the composition of Reference Example 1, the platinum concentration of the catalyst (C) was set to 20 mass ppm. In this case, the organopolysiloxane composition did not harden in the heat treatment at 120° C.×30 seconds, but became oily. That is, hardening is insufficient. In addition, even after aging at 25° C. for 1 day, the hardening was not sufficient, and after wiping the coated surface, the finger marks were clear. Moreover, due to the large amount of migration, the sclerosing property and silicone migration property are poor.
另外，如表2所示，比較例3及比較例4是在比較例1的組成物中調配1質量份兩末端具有丙烯酸基的矽氧烷（10）或丙烯酸的組成物。該組成物含有含丙烯酸基的矽氧烷或丙烯酸，但硬化性及密接性差，矽酮遷移性與比較例1同等差。另外，剝離力較參考例1高，殘留接著率亦低。比較例2是調配了100質量份兩末端具有乙烯基、側鏈具有丙烯酸基的甲基聚矽氧烷（9）的組成物。該矽氧烷在一分子中平均具有10個丙烯酸基。該組成物含有含乙烯基及丙烯酸基的矽氧烷，但硬化性及密接性差，矽酮遷移性與比較例1同等差。另外，剝離力較參考例1高，殘留接著率亦低。Moreover, as shown in Table 2, the comparative example 3 and the comparative example 4 are the compositions which mixed 1 mass part of the siloxane (10) or acrylic acid which has an acrylic group at both ends to the composition of the comparative example 1. This composition contains acrylic group-containing siloxane or acrylic acid, but has poor hardenability and adhesion, and is equally inferior to Comparative Example 1 in silicone migration. In addition, the peeling force was higher than that of Reference Example 1, and the residual adhesion rate was also low. Comparative Example 2 is a composition prepared by mixing 100 parts by mass of methylpolysiloxane (9) having vinyl groups at both ends and acrylic groups in side chains. The siloxane has an average of 10 acrylic groups in one molecule. This composition contains vinyl- and acrylic-group-containing siloxanes, but has poor curability and adhesion, and is equally inferior to Comparative Example 1 in silicone migration. In addition, the peeling force was higher than that of Reference Example 1, and the residual adhesion rate was also low.
與此相對，如表1所示，實施例1～實施例8是含有在兩末端具有乙烯基、在側鏈具有特定量丙烯酸基的甲基聚矽氧烷的有機聚矽氧烷組成物。該些實施例1～實施例8中，藉由具有特定量的丙烯酸基或甲基丙烯酸基的含乙烯基的有機聚矽氧烷作為（A）成分，儘管（C）觸媒的鉑濃度少，但充分硬化。因此，即使擦拭硬化皮膜的塗敷面，亦幾乎不會留下指痕，矽酮轉移量亦少。另外，剝離力與殘留接著率與參考例1同等。因此，藉由含有本申請案的（A）成分，組成物的硬化性提高，能夠以少的鉑濃度進行加成反應。In contrast, as shown in Table 1, Examples 1 to 8 are organopolysiloxane compositions containing methylpolysiloxane having vinyl groups at both ends and a specific amount of acrylic groups in side chains. In these Examples 1 to 8, a vinyl group-containing organopolysiloxane having a specific amount of acrylic group or methacrylic group is used as the component (A), although the platinum concentration of the catalyst (C) is small. , but fully hardened. Therefore, even if the coated surface of the hardened film is wiped, almost no finger marks are left, and the amount of silicone transfer is small. In addition, the peeling force and the residual adhesion rate were the same as those of Reference Example 1. Therefore, by containing (A) component of this application, the curability of a composition improves, and an addition reaction can be performed with a small platinum density|concentration.
特別是實施例3中使用的甲基聚矽氧烷（3）的D單元的數量為220，含有2.5個具有丙烯酸基的矽氧烷單元。另外，實施例5中使用的甲基聚矽氧烷（5）的分子量與甲基聚矽氧烷（2）相同，在側鏈上具有2個乙烯基。即使是含有此種甲基聚矽氧烷的組成，硬化性及密接性亦良好。另外，實施例6的組成物是並用了具有丙烯酸基及乙烯基的甲基聚矽氧烷（3）以及不具有丙烯酸基而具有乙烯基的甲基聚矽氧烷（8）的組成。在該組成物中，硬化性亦良好，矽酮轉移量亦少。另外，剝離力及殘留接著率與參考例1相同。因此，即使是先前的含有含乙烯基的有機聚矽氧烷的組成，藉由含有本申請案的（A）成分，亦以少的鉑觸媒充分地促進加成反應。In particular, the methylpolysiloxane (3) used in Example 3 had a number of D units of 220, and contained 2.5 siloxane units having an acrylic group. In addition, the molecular weight of the methyl polysiloxane (5) used in Example 5 is the same as that of the methyl polysiloxane (2), and it has two vinyl groups in the side chain. Even in the composition containing such a methyl polysiloxane, sclerosis and adhesiveness are good. Moreover, the composition of Example 6 is a composition which used the methyl polysiloxane (3) which has an acrylic group and a vinyl group, and the methyl polysiloxane (8) which does not have an acrylic group but has a vinyl group in combination. In this composition, the curability is also good, and the amount of silicone transfer is small. In addition, the peeling force and the residual adhesion rate were the same as those of Reference Example 1. Therefore, even in the composition containing the conventional vinyl group-containing organopolysiloxane, the addition reaction is sufficiently accelerated with a small platinum catalyst by containing the component (A) of the present application.
即，藉由調配本發明的（A）成分，即使（C）鉑族金屬系觸媒為低於100質量ppm的低鉑濃度，組成物亦能夠充分硬化，而能夠獲得與以100質量ppm硬化的情況同等的剝離特性。That is, by blending the component (A) of the present invention, even if the platinum group metal-based catalyst (C) is at a low platinum concentration of less than 100 mass ppm, the composition can be sufficiently cured, and it is possible to obtain the same performance as curing at 100 mass ppm. The same peel characteristics of the case.
本發明的有機聚矽氧烷組成物雖然鉑族金屬系觸媒量少，但充分硬化，能夠形成具有與先前的加成型組成物同等的剝離力的硬化皮膜，而適合作為提供剝離紙及剝離膜用的硬化皮膜的組成物。本發明的有機聚矽氧烷組成物即使在先前難以硬化的條件下亦可硬化，由於鉑族金屬觸媒量少，能夠大幅降低製造成本。另外，對於含有觸媒毒的基材亦可藉由加成反應進行硬化。The organopolysiloxane composition of the present invention has a small amount of platinum group metal-based catalyst, but is sufficiently cured to form a cured film having a peeling force equivalent to that of the conventional addition-type composition, and is suitable for providing release paper and peeling The composition of the cured film for film. The organopolysiloxane composition of the present invention can be cured even under previously difficult conditions, and since the amount of platinum group metal catalyst is small, the production cost can be greatly reduced. In addition, the substrate containing catalyst poison can also be hardened by addition reaction.
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| JP6330736B2 (en) * | 2015-06-11 | 2018-05-30 | 信越化学工業株式会社 | Organopolysiloxane composition and method for producing the same, mist inhibitor, and solvent-free release paper or release film silicone composition |
| JP6555196B2 (en) * | 2016-06-17 | 2019-08-07 | 信越化学工業株式会社 | Addition-curable liquid silicone rubber composition |
| JP6723934B2 (en) * | 2017-01-25 | 2020-07-15 | 信越化学工業株式会社 | Silicone composition, release paper and release film |
| JP6754318B2 (en) * | 2017-05-10 | 2020-09-09 | 信越化学工業株式会社 | Silicone resin composition for die bonding, die bonding material and optical semiconductor device |
| TWI801443B (en) * | 2017-10-27 | 2023-05-11 | 美商陶氏有機矽公司 | Curable polyorganosiloxane composition, cured body obtained by curing said compositions, and electronic device comprising the same |
| CN112334561B (en) * | 2018-06-28 | 2023-08-22 | 信越化学工业株式会社 | Organopolysiloxane composition for release paper or release film |
-
2021
- 2021-05-31 TW TW110119712A patent/TW202200674A/en unknown
- 2021-06-03 US US18/001,319 patent/US20230250236A1/en active Pending
- 2021-06-03 EP EP21821163.9A patent/EP4166613A1/en active Pending
- 2021-06-03 CN CN202180040771.1A patent/CN115698182A/en active Pending
- 2021-06-03 WO PCT/JP2021/021153 patent/WO2021251255A1/en unknown
- 2021-06-03 KR KR1020227045249A patent/KR20230023665A/en active Search and Examination
- 2021-06-03 JP JP2022530515A patent/JP7455974B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230023665A (en) | 2023-02-17 |
| JP7455974B2 (en) | 2024-03-26 |
| JPWO2021251255A1 (en) | 2021-12-16 |
| WO2021251255A1 (en) | 2021-12-16 |
| US20230250236A1 (en) | 2023-08-10 |
| EP4166613A1 (en) | 2023-04-19 |
| CN115698182A (en) | 2023-02-03 |
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